Nitrogen-carbon bonds are ubiquitous in products ranging from chemical feedstock to pharmaceuticals. Since ammonia is among the largest volume and least expensive bulk chemicals, one of the greatest challenges of synthetic chemistry is to find atom efficient processes capable of combining NH3 with simple organic molecules to create nitrogen-carbon bonds. Transition metal complexes can readily render a variety of N—H bonds, including those of primary and secondary amines, reactive enough to undergo functionalization. However, apart from a few exceptions, ((E. G. Bryan, B. F. G. Johnson, K. Lewis, J. Chem. Soc., Dalton Trans. 1977, 1328-1330; G. L. Hillhouse, J. E. Bercaw, J. Am. Chem. Soc. 1984, 106, 5472-5478; A. L. Casalnuovo, J. C. Calabrese, D. Milstein, Inorg. Chem. 1987, 26, 971-973; M. M. B. Holl, P. T. Wolczanski, G. D. Van Duyne, J. Am. Chem. Soc. 1990, 112, 7989-7994; J. Zhao, A. S. Goldman, J. F. Hartwig, Science 2005, 307, 1080-1082; Y. Nakajima, H. Kameo, H. Suzuki, Angew. Chem. 2006, 118, 964-966; Angew. Chem. Int. Ed. 2006, 45, 950-952. A non-metallic system has recently been reported to cleave NH3 under mild experimental conditions: G. D. Frey, V. Lavallo, B. Donnadieu, W. W. Schoeller, G. Bertrand, Science 2007, 316, 439-441; A. L. Kenward, W. E. Piers, Angew. Chem. 2008, 120, 38-42; Angew. Chem. Int. Ed. 2008, 47, 38-41; and J. M. Lynam, Angew. Chem. 2008, 120, 831-833; Angew. Chem. Int. Ed. 2008, 47, 843-845)) metals usually react with ammonia to afford supposedly inert Lewis acid-base complexes, as first recognized in the late 19th century by Werner (A. Werner, Z. Anorg. Chem. 1893, 3, 267). Consequently, the catalytic functionalization of NH3 has remained elusive until the recent discovery by Hartwig (Q. Shen, J. F. Hartwig, J. Am. Chem. Soc. 2006, 128, 10028-10029) and Buchwald (D. S. Surry, S. L. Buchwald, J. Am. Chem. Soc. 2007, 129, 10354-10355) of the palladium catalyzed coupling of aryl halides with ammonia in the presence of a stoichiometric amount of base. An even more appealing process would be the addition of NH3 to carbon-carbon multiple bonds, a process that ideally occurs with 100% atom economy (R. Severin, S. Doye, Chem. Soc. Rev. 2007, 36, 1407-1420; S. Matsunaga, J. Synth. Org. Chem. Japan 2006, 64, 778-779; K. C. Hultzsch, Adv. Synth. Catal. 2005, 347, 367-391; M. Beller, J. Seayad, A. Tillack, H. Jiao, Angew. Chem. 2004, 116, 3448-3479; Angew. Chem. Int. Ed. 2004, 43, 3368-3398; F. Alonso, I. P. Beletskaya, M. Yus, Chem. Rev. 2004, 104, 3079-3159; P. W. Roesky, T. E. Müller, Angew. Chem. 2003, 115, 2812-2814; Angew. Chem. Int. Ed. 2003, 42, 2708-2710; F. Pohlki, S. Doye, Chem. Soc. Rev. 2003, 32, 104-114; T. E. Mailer, M. Beller, Chem. Rev. 1998, 98, 675-703).
Although, various catalysts have been used to effect the so-called hydroamination reaction, which include alkali metals, ((C. G. Hartung, C. Breindl, A. Tillack, M. Beller, Tetrahedron 2000, 56, 5157-5162; P. Horrillo-Martinez, K. C. Hultzsch, A. Gil, V. Branchadell, Eur. J. Org. Chem. 2007, 3311-3325; S. Datta, M. T. Gamer, P. W. Roesky, Organometallics 2008, 27, 1207-1213); early transition metals (P. W. Roesky, Z. Anorg. Allg. Chem. 2006, 632, 1918-1926; A. L. Odom, Dalton Trans. 2005, 225-233; N. Hazari, P. Mountford, Acc. Chem. Res. 2005, 38, 839-849; I. Bytschkov, S. Doye, Eur. J. Org. Chem. 2003, 935-946; E. Smolensky, M. Kapon, M. S. Eisen, Organometallics 2007, 26, 4510-4527; M. Dochnahl, K. Löhnwitz, J.-W. Pissarek, M. Biyikal, S. R. Schulz, S. Schön, N. Meyer, P. W. Roesky, S. Blechert, Chem. Eur. J. 2007, 13, 6654-6666); late transition metals (J. Zhang, C.-G. Yang, C. He, J. Am. Chem. Soc. 2006, 128, 1798-1799; K. Komeyama, T. Morimoto, K. Takaki, Angew. Chem. 2006, 118, 3004-3007; Angew. Chem. Int. Ed. 2006, 45, 2938-2941; F. E. Michael, B. M. Cochran, J. Am. Chem. Soc. 2006, 128, 4246-4247; A. M. John, N. Sakai, A. Ridder, J. F. Hartwig, J. Am. Chem. Soc. 2006, 128, 9306-9307; A. Takemiya, J. F. Hartwig, J. Am. Chem. Soc. 2006, 128, 6042-6043; A. R. Chianese, S. J. Lee, M. R. Gagné, Angew. Chem. 2007, 119, 4118-4136; Angew. Chem. Int. Ed. 2007, 46, 4042-4059; G. Kovács, G. Ujaque, A. Lledós, J. Am. Chem. Soc. 2008, 130, 853-864); d-block elements (N. Meyer, K. Lohnwitz, A. Zulys, P. W. Roesky, M. Dochnahl, S. Blechert, Organometallics 2006, 25, 3730-3734; X. Y. Liu, C. H. Li, C. M. Che, Org. Lett. 2006, 8, 2707-2710; A. Zulys, M. Dochnahl, D. Hohmann, K. Lohnwitz, J. S. Hellmann, P. W. Roesky, S. Blechert, Angew. Chem. 2005, 117, 7972-7976; Angew. Chem. Int. Ed. 2005, 44, 7794-7798) and f-block elements, (D. V. Gribkov, K. C. Hultzsch, F. Hampel, J. Am. Chem. Soc. 2006, 128, 3748-3759; D. Riegert, J. Collin, A. Meddour, E. Schulz, A. Trifonov, J. Org. Chem. 2006, 71, 2514-2517; E. Arnea, M. S. Eisen, Coord. Chem. Rev. 2006, 250, 855-859; S. Hong, T. J. Marks, Acc. Chem. Res. 2004, 37, 673-686; T. Andrea, M. S. Eisen, Chem. Soc. Rev. 2008, 37, 550-567; I. Aillaud, J. Collin, J. Hannedouche, E. Schulz, Dalton Trans. 2007, 5105-5118; M. Rastätter, A. Zulys, P. W. Roesky, Chem. Eur. J. 2007, 13, 3606-3616) none are effective for the hydroamination of alkynes and allenes when NH3 is used as the amine partner.
Despite recent advances, there still remains a need for an atom-efficient process capable of combining abundant NH3 and amines with simple organic molecules to create nitrogen-carbon bonds as well as allenes. The present invention fulfills this and other needs.